JPS6157548A - Nitroethylene compound and its synthesis - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is alkyl, cycloalkyl, or aryl; X ia halogen, n is 2-4). EXAMPLE:2-[(3-Formamido)propyl]thio-2-chloro-nitroethylene. USE:A raw material for agricultural chemicals. PREPARATION:A compound shown by the formula II (X<1>-X<3> are halogen) is reacted with a compound shown by the formula III in a solvent (e.g., methanol) in the presence of a base (e.g., sodium methoxide), to give a compound shown by the formula I. The reaction is usually carried out at <=100 deg.C, preferably -10- 50 deg.C for 0.5-10hr, preferably for 1-5hr. An amount of the compound shown by the formula III used is usually 0.1-2mol, preferably 0.3-1.2mol based on 1mol compound shown by the formula II, and an amount of the base used is usually 1.0-3.0mol, preferably 1.8-2.3mol based on 1mol compound shown by the formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel nitroethylene compound and a method for synthesizing the same.

Nitroethylene compounds are useful compounds as raw materials for agricultural chemicals.

[Conventional technology]

No literature has been found so far describing the nitroethylene compound of the present invention and its synthesis method.

[Problem that the invention seeks to solve]

The present invention provides a novel nitroethylene compound and an industrially advantageous method for producing this compound.

[Means for solving problems]

The present invention is.

General formula (1[) #, . . . represents a group, and X represents a gen atom.

Further, n represents 2.3 or 4. ) and 1,1.1- nitroethylene compounds represented by the general formula (1) % formula % (wherein Xi, X2 and x3 in formula 1 represent the same or different halogen atoms)
A trihalo-2-nitroethane compound in a solvent in the presence of a base.

General formula (n) (However, in formula 1, R represents an alkyl, cycloalkyl, or aryl group, and n represents 2.3''! or 4.)
The general formula (I
This is a method for synthesizing a nitroethylene compound represented by n).

1,1.1-)dihalo-2- represented by general formula (1)
In the nitroethane compound, the halogen atoms represented by + X' + X2 and x3 are chlorine atom, bromine atom,
Either a fluorine atom or an iodine atom may be used, and X
'l! " and x3 may be the same halogen atom or different halogen atoms. Specific examples include 1.1.1-1lichloro-2-nitroethane, 1-bromo1.1 - diku-a-2-nitroethane,
1-chloro-1,1-dibromo-2-nitroethane, 1
．． 1-dichloro-1-iodo-2-nitroethane, 1-
Chloro-1+1-short-2-nitroethane, 1,1
-dichloro-1-fluoro-2-nitroethane, 1-chloro-1,1-difluoro-2-nitroethane, 1,1
-dibromo-1-iodo-2-nitroethane, 1-bromo-1,1-short-2-nitroethane, 111-sifukumo-1nitrooro-2-nitroethane.

1-ProT--1.1-difluoro-2-nitroethane, 1,1.1-)dibromo-2-nitroethane.

1.1.1-triiodo-2-nitroethane, 1,1.
Examples include 1-trifluoro-2-nitroethane. Among these, 1% is 11111-) because it is an industrially easily available compound! J Claw 2-
Nitroethane is useful.

Cholera 1.1.1-) The dihalo-2-nitroethane compound can be easily synthesized by the method of Koji. For example, a method of reacting vinylidene chloride with dinitrogen tetroxide and chlorine in a solution [J.

Org-Chem, 25 1312 (1960)),
Method of reacting vinylidene chloride and nitrile chloride (C
There is A5 upper 11'121)).

In each group represented by R in formula (1), the alkyl group includes methyl, ethyl, propyl, butyl, hexyl,
Examples of the cyclohexyl group include those having 1 to 12 carbon atoms such as octyl.

Examples of the aryl group include those having 5 to 7 carbon atoms such as cyclopentyl, cyclohexyl, and cyclohexyl, and examples of the aryl group include phenyl and naphthyl. General formula (I
I). N-(mercaptoalkyl)-carboxylic acid amide compound.

These are industrially available compounds, and specific examples thereof include:

N-(2-mercaptoethyl)-acetamide.

N-(3-mercaptopropyl)-acetamide.

N-(4-Mercaptobutyl)-acetamide.

N-(2-mercaptoethyl)-propionic acid amide.

N-(3-mercaptopropyl)-propionic acid amide.

N-(4-Mercaptobutyl)-propionic acid amide.

N-(2-mercaptoethyl)-cyclohexanecarboxylic acid amide.

N-(j-mercaptopropyl)-cyclohexanecarboxylic acid amide.

N-(4-mercaptobutyl)-cyclohexanecarboxylic acid amide.

N-(2-mercaptoethyl)-benzoic acid amide.

N-(s-mercaptopropyl)-benzoic acid amide.

N-(4-Mercaptobutyl)-benzoic acid amide.

N-(3-mercaptopropyl)-formamide.

N-(3-mercaptopropyl)-1-butyric acid amide.

Examples include N-(3-mercaptopropyl)-n-butyric acid amide.

The amount of these N-(mercaptoalkyl)-carboxylic acid amide compounds used is usually 0.1 to 2 mol per 1 mol of the 1-to-17-halo-2-nitroethane compound.
Preferably it is 0.6 to 1.2 mol.

The bases that can be used in the present invention include:

Sodium methoxide, sodium ethoxide.

Alcolades of alkali metals such as potassium methoxide or potassium ethoxide; hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide; alkaline earth metals such as calcium hydroxide, barium hydroxide or magnesium hydroxide. Hydroxides and the like are useful.

The amount of these bases to be used is i, 1.1-
The amount is usually 1.0 to 3.0 mol, preferably 1.8 to 2.3 mol, per mol of the trihalo-2-nitroethane compound.

The reaction in the present invention is carried out in a solvent. The solvent that can be used is one that can dissolve both raw materials and the base at the same time and is inert to the reaction.

All are useful.

Specific examples include methanol and ethanol.

Examples include lower aliphatic alcohols such as 1-glopanol, n-glopanol, 1-butanol, and n-butanol, water, dimethyl sulfoxide, acetonitrile, and dimethylformamide. Among these, from the viewpoint of industrial implementation, it is particularly preferable to use lower aliphatic alcohols as the solvent.

There is no need to place any special restrictions on the method of reacting the 1,1.1-)dihalo-2-nitroethane compound and the N-(merodetoalkynolycarpho'')amide compound in the present invention. For example, a method in which a base is added to a solution in which both raw materials are dissolved in a solvent, or an N-(mercaptoalkyl)-carboxylic acid amide compound is prepared by reacting the N-(mercaptoalkyl)-carboxylic acid amide and a base in advance in a solvent. A method can be employed in which the compound is converted into a thiolate compound and then reacted with a 1,1.1-1rehalo-2-nitroethane compound.

The reaction of the present invention can be carried out at a temperature usually below 100°C, preferably at a temperature of -10 to 50°C, for 0.5 to 10 hours, preferably 1 to 5 hours.

After the reaction is complete, the target product is isolated and purified by filtration and concentration.

This can be easily carried out by appropriately employing operations such as extraction or column separation.

Specific examples of the compound represented by the above general formula (1) are as follows.

2-((3-formamido)furobylcothio-2-chloro-nitroethylene, 2-[:(3-acetamido)furobylcothio-2-chloro-nitroethylene, 2-((
s-propionic acid amido)propylcutio 2-chloro-nitroethylene, 2-((3-n-butyric acid amido)propylcutio 2-chloro-nitroethylene, 2-((3
-1-butyric acid amyl)”)7’lopyl]thio-2-chloro-
Nitroethylene, 2-((3-cyclohexanecarboxylic acid amido)furobylcothio-2-f'loronitroethylene, 2-((3-benzoic acid amido)propyl)thio-
2-chloro-nitroethylene, 2-((2-formamido)ethylcothio-2-chloro-nitroethylene, 2-
((2-acetamido)ethyl]fyF-2-chloro-
Nitroethylene, 2-[(2-propionic acid amido)ethylcothio-2-chloro-nitroethylene, 2-1:(
3-formamide) furovircuthio 2-promonitroethylene, 2-((3-acetamido)propylcothio-2-promonitroethylene, 2-C(3-propionamide)propylcutio2-pro7-nitroethylene, 2-C(4-formamido)butylkothio-
2-chloro-nitroethylene.

Examples include 2-((4-acetamido)butylcothio-2-chloro-nitroethylene, 2-((a-7'lohionamide)butylcothio-2-chloro-nitroethylene, etc.). Either one or a mixture thereof may be used.

〔Example〕

Next, seven examples of the present invention will be described. Note that the yield of the target product on each side is based on +11111-trinos rho-2-nitroethane compound.

Example 1 Methanol 50m/! , 1,1,1-trichloro-2
-7.11 parts of nitroethane were added and the mixture was cooled to -20°C.

While stirring this solution, add 5.3f of N-(3-mercaptopropyl)-acetamide and 3f of caustic soda.
．． A solution prepared by dissolving 21 in 50 mJ of methanol was slowly added dropwise over 60 minutes. Next, after reacting for 30 minutes, 100 ml of water was added and 100 d of methylene chloride was added.
After extracting 4 times with
(ethyl acetate). As a result, 2-(3-(
Acetamide) furovircothio-2-chloro-nitroethylene (3.3f, yield 34g) was obtained as a viscous oil.

Mass spectrum M+1=259° Elemental analysis value (%): CL; 35.10. H; 4.62°N; 11.80. CL; 13.99; (C7HHC
Theoretical value as 2N2038 @) 0; 35.22,
H; 4.65, N; 11.74C1; 14.85
) Example 2 Purified product 6.41 was obtained by conducting an experiment in the same manner as in Example 1, except that sodium methoxide 4.31 was used instead of caustic soda 3.21. When the same analysis as in Example 1 was carried out, the purified product was confirmed to be 2-[self-(acetamido)propylcothio-2-chloro-nitroethylene.

Example 3 An experiment was conducted in the same manner as in Example 1, except that caustic potash 4.51 was used instead of caustic soda 3.22, to obtain purified product 3.31. When the same analysis as in Example 1 was carried out, the purified product was confirmed to be 2-1:3-(acetamido)propylcothio-2-chloro-nitroethylene.

Example 4 N-(3-mercaptopropyl)-acetamide 5.3
An experiment was carried out in the same manner as in Example 1, except that 4.81% of N-(2-mercaptoethyl)-acetamide was used instead of 1. As a result, 2-[2-(acetamido)ethylcothio-2-chloro-nitroethylene (2,9f3
2%) t"gain 7'c.

Mass spectrum RIL+1=225゜Elemental analysis value (%
) C; 31.53. H;4.00. N;12.31.
Cjt;15.12 (Theoretical value@) As C6H9ctN2o3s, C;3
2.07°H; 4.04. N;12.47. Ct;1
5.78) Example 5 N-(3-mercaptopropyl)-acetamide 5.3
1, N-(3-mercaptopropyl)-propionic acid amide 5.9? The same operation as in Example 2 was performed except that . As a result, 2-[6-(propionamide)propylcothio-2-chloro-nitroethylene (3
，! M' 35%) was obtained.

Mass spectrum M+1=253 Elemental analysis position) C; 38.37. H;5.01. N;1
0.97. Ct; 13.51 (theoretical value (%)
CL8H13Ct N203 S as C; 38.0
2°H; 5.18. N;11.09. Ct;14.
03) Example 6 N-(3-mercaptopropyl)-acetamide 5.3
2, N-(3-mercaptopropyl)-cyclohexanecarboxylic acid amide 8.0? The same operation as in Example 2 was performed except that . As a result, 2-(S-
(Cyclohexanecarboxamide) furovircutio 2-chloro-nitroethylene (3,75' 30%)
I got it.

Mass spectrum M+1 = 307° Elemental analysis value (%) C; 47.12. H;6.20. N;
9.25. Ol; 10.98 (Theoretical value (%) 012 Hts CL t N203
As S, f:! ;46.97°H;6.24. N;
9.13. C4; 11.56) Example 7 N-(3-mercaptopropyl)-acetamide 5.3
In place of 1, N-(3-mercaptopropyl)-benzoic acid amide 7.8? The same operation as in Example 2 was performed except that . As a result, 2-(3=(benzamido)propylcothio-2-chloro-nitroethylene (3,8p
32%) was 4.

Mass spectrum M+1=301 Elemental analysis value (%) C; 47.63. H;4.28. N;
9.10. C1; 11.00° (theoretical value (a) C12N13 CL N203S, C; 47.92°H; 4.36.N; 9.32.CL
;11.79) Example 8 N-(5-mercaptopropyl)-acetamide 5.3
The same operation as in Example 2 was performed except that 5.91% of N-(4-mercaptobutyl)-acetamide was used instead of 1. As a result, 2-(4-(acetamido)butylcothio-2-chloro-nitroethylene (3,55' 3
5ch) was obtained.

Mass spectrum M+1=253° Elemental analysis value (%) CL; 37.87. H;5.33. N
;10.86. C1; 14.51 (theoretical value (4) as CsHt3C4N203S, f:
! ;3.802°H;5.18. N;11.03. C1
;14.03) Example 9 N-(3-mercaptopropyl)-acetamide 5.3
The same operation as in Example 2 was performed except that 4.71 N-(3-mercaptopropyl)-formamide was used in place of 1. As a result, 2-(3-(formamido)propylcothio-2-chloro-nitroethylene (2,sr 2
a%) was obtained.

Claims (2)

[Claims] (1) General formula (III) ▲Mathematical formulas, chemical formulas, tables, etc.▼・・・(III) (However, in the formula, R represents an alkyl, cycloalkyl, or aryl group, and X represents a halogen atom. and n represents 2, 3 or 4). (2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I
) (However, in the formula, X^1, X^2 and X^3 represent the same or different halogen atoms.) 1,1 represented by
, 1-trihalo-2-nitroethane compound in the presence of a base in a solvent, the general formula (II) ▲There are numerical formulas, chemical formulas, tables, etc.▼・・・・・・(II) represents an alkyl, cycloalkyl or aryl group, and n represents 2, 3 or 4. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(III) (However, in the formula, R, X, and n have the same meanings as above.) A method for synthesizing a nitroethylene compound.